S-diphenylmethyl-dithiophosphates

ABSTRACT

S-diphenylmethyl-dithiophosphate of the formula   WHEREIN R1 represents alkyl with 1 to 5 carbon atoms R2 represents alkyl with 1 to 5 carbon atoms, alkylthioalkyl with 1 to 5 carbon atoms in each of the moieties, alkenyl with 3 to 5 carbon atoms or alkinyl with 3 to 5 carbon atoms, and R3 to R12 each represents hydrogen, halogen or alkoxy with 1 to 5 carbon atoms, a process for their manufacture and their use in pest control.

United States Patent 91 Kristiansen 1 S-DIPHENYLMETI-IYL-DITI-IIOPIIOSPIIATES [75] Inventor: Odd Kristiansen, Reinach,

Basel-Land, Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Jan. 28, 1974 211 App]. No.: 437,414

[30] Foreign Application Priority Data Feb. 7, 1973 Switzerland 1755/73Dec. 20, 1973 Switzerland 17773/73 [52] US. Cl. 260/948; 260/951;260/956; 260/963; 260/973; 424/216; 424/217; 424/219; 424/225 FOREIGNPATENTS OR APPLICATIONS 893,339 4/1962 United Kingdom 260/963 51 May 20,1975 Primary ExaminerLorraine A. Weinberger Assistant ExaminerRichard L.Raymond Attorney, Agent, or FirmFrederick H. Rabin [57] ABSTRACTS-diphenylmethyl-dithiophosphate of the formula wherein R representsalkyl with l to 5 carbon atoms R represents alkyl with l to 5 carbonatoms, alkylthioalkyl with 1 to 5 carbon atoms in 'each of the moieties,alkenyl with 3 to 5 carbon atoms or alkinyl with 3 to 5 carbon atoms,and R to R each represents hydrogen, halogen or alkoxy with 1 to 5'carbon atoms, a process for their manufacture and their use in pestcontrol.

8 Claims, No Drawings 1 S-DIPHENYLMETHYL-DITHIOPHOSPHATES The presentinvention relates to S-diphenylmethyldithiophosphates, a process fortheir manufacture, and to their use in pest control.

The S-diphenylmethyl-dithiophosphate have the formula R R R R R FIQRS RR S R3 R wherein R represents alkyl with l to carbon atoms R representsalkyl with l to 5 carbon atoms, alkylthioalkyl with l to 5 carbon atomsin each of the moieties, alkenyl with 3 to 5 carbon atomsor alkinyl with3 to 5 carbon atoms, and R to R each represents hydrogen, halogen oralkoxy with 1 to 5 carbon atoms.

Halogen is to be understood as meaning fluorine, chlorine, bromineand/or iodine.

The alkyl, alkoxy, alkylthioalkyl, alkenyl or alkinyl groups which arepossible for R to R can be straightchain or branched. Examples of suchgroups include: methyl, methoxy, methylthiomethyl, ethyl, ethoxy,propyl, isopropyl, n-butyl, iso-butyl, sec. and tert. butyl, n-pentyland isomers thereof, allyl, propargyl.

Preferred compounds on account of their action are those of the formulaI, wherein R represents ethyl, R represents alkyl, -CH -SCH orpropargyl, R R R R R R and R each represents hydrogen and R R and R eachrepresents hydrogen, chlorine or methoxy.

Particularly preferred compounds, however, are those of the formula I,wherein R represents ethyl, R represents n-propyl, n-butyl or iso-butyl,R R R R R R and R each represents hydrogen and R R and R each representshydrogen or chlorine.

The compounds of the formula I can be manufactured by the followingmethod which is known per se:

12 l 4 (III) I MeHal in the formulae II to IV, the symbols R to R havethe meanings given for the formula I and Hal represents a halogen atom,in particular chlorine, or bromine, and Me represents an alkali metal,in particular sodium or potassium.

The process is carried out at normal pressure, at a temperature between0 to 150C, preferably between 20 to C, and in solvents or diluents whichare inert towards the reactants. Examples of suitable solvents anddiluents are: aromatic hydrocarbons, e.g.' benzene, toluene, halogenatedhydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene,chlorinated -alkanes with 1 to 3 carbon atoms, ethers, e.g. dioxan,tetrahydrofuran; esters, e.g. ethyl acetate; ketones, e.g. acetone,methyl ethyl ketone, diethyl ketone; nitriles, e.g. acetonitrile etc. v

The compounds of the formula I exhibit a broad biocidal activity and canbe used for the control of a variety of plant and animal pests.

In particular they are suitable for combating insects of the families:Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae,Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae,Diaspididae, Pseudococcidae, Chrysomelisae, Coccinellidae, ,Bruchidae,Scarabaeidae, Dermestidae, Tenebrionidae,

Curculionidae, Tineidae, Noctuidae, Lymantriidae PyralidaefGalleridae,Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae,Pulicidae as well as Acaridae of the families: Ixodidae, Argasidae,Tetranchidae, Dermanyssidae.

By addition of other indecticides and/or acaricides it is possible toimprove substantially the insecticidal or acaricidal action and to adaptit to given circumstances.

Examples of suitable additives are: organic phosphorus compounds,nitrophenols and derivatives thereof; formamidines; ureas; carbamatesand chlorinated hydrocarbons.

In addition to the above mentioned properties, the compounds of theformula I also exhibit a microbiocidal action. Thus a number of thesecompounds display bactericidal action. But they are active chieflyagainst fungi, especially against phytopathogenic fungi belonging to thefollowing classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes,Denteromycetes.

The compounds of the formula [also exhibit a fungitoxic action againstfungi which attack the plants from the soil. The new active substancesare also suitable for treating seeds, fruit, tubers etc. from attack byfungus infections. The compounds of the formula I are also suitable forcombating phytopathogenic nematodes.

The compounds of the formula I may be used as pure active substance ortogether with suitable carriers and- /or additives. Suitable carriersand additives can be solid or liquid and correspond to the substancesconventionally used in formulation technology, for example natural orregenerated substances, solvents, dispersants, wetting agents,adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of the formula I may be processed todusts, emulsion concentrates, granules, dispersions, sprays, tosolutions or suspensions, in the conventional formulation which iscommonly employed in application technology. Mention is also to be madeof cattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances can take, and be used in, the following forms: Solid forms:

dusts, tracking agents, granules, coat'ed granules, impregnated granulesand homogeneous granules. Liquid forms:

21. active substances which are dispersible in water: wettable powders,pasts, emulsions:

b. solutions.

The content of active substance in the above described agents is between0.1 to 95%, in which connection it should be mentioned that, in the caseof application from aircraft or some other suitable means ofapplication, it is possible to use concentrations of up to 99.5% or evenpure active substance.

The active substances of the formula I can, for example, be formulatedas follows:

Dusts The following substances are used to manufacture (a) a 5% and (b)a 2% dust: a. 5 parts of active substance 95 parts of talcum b. 2 partsof active substance 1 partof highly disperse silicic acid 97 parts oftalcum. The active substances are mixed with the carriers and ground.

Granules The following substances are used to produce 5% granules:

5 parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.30.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The resulting solution is sprayed on kaolin, and the acetoneis subsequently evaporated in vacuo.

Wettable powder The following constituents are used for the preparationof (a) a 40%, (b) and (c) a 25%, and (d) a 10% wettable powder:

a. 40 parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutyl-naphthalene sulphonate,

54 parts of silicic acid.

b. 25 parts of active substance,

4.5 parts of calcium lignin sulphonate,

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulphonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin.

c. 25 parts of active substance,

2.5,parts of isooctylphenoxy-polyoxyethylene-ethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

8.3 parts of sodium aluminium silicate,

16.6 parts of kieselguhr,

46 parts of kaolin.

d. 10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suit- I able mixers, withthe additives, the mixture being then ground in the appropriate millsand rollers. Wettable powders are obtained which can be diluted withwater to give suspensions of any desired concentration.

Emulsifiable concentrates The following substances are used to produce(a) a 10% and (b) a 25% emulsifiable concentrate:

a. 10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylaryl sulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene,

25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarylsulphonate/fatty alcoholglycol ether mixture,

5 parts of dimethylformamide,

57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concentration.

Spray The following constituents are used to prepared a 5% spray:

5 parts of active substance,

1 part of epichlorohydrin, 94 parts of benzene (boiling limits 160l90C).

EXAMPLE 1 Manufacture of theO-ethyl-S-propyl-S-diphenylmethyl-dithiophosphoric acid ester 19 g ofthe potassium salt of O-ethyl-S-propyl-dithiophosphoric acid are addedat room temperature to a solution of 18.5 g of bromodiphenylmethyl in mlof absolute acetonitrile. The reaction mixture is subsequently stirredand filtered. After the filtrate has been evaporated, the residue istaken up in either, washed twice with 100 ml of water each time and theorganic phase is dried with sodium sulphate, to yield as productCl*-CHC1 crude O-ethyl-S-propyl-S-diphenylmethylo dithiophosphoric acidester which can be purified by S 5 1,5974 chromatography through asilica gel column. Refractive index: n 1.5878. 0=POC H5 The followingcompounds are also manufactured in I analogous manner: SC H (n) I 111,5935 5 S n 1,5991 l :P-OC H O=Il SCli O I 2 5 SC H (n) EXAMPLE 2 o A.Insecticidal ingest poison action 20 Cotton and potato plants weresprayed with a 0.05%

I nD 1,6057 aqueous emulsion (obtained from'a 10% emulsifiable Sconcentrate). After the coating had dried, the cotton plants werepopulated with Spodoptera litroralis or Heliothis virescens larvae L andthe potato plants with Col- 5 3O orado potato bettle larvae(Leptinotarsa decem- SCH CECH lineata). The test was carried out at 24Cand 60% rela- 2 tive humidity. In the above test, the compoundsaccording to Example 1 displayed good ingest poison action againstSpodoptera littoralis. Heliothis and Leptinotarsa decemlineata larvae.

B. Systemic insecticidal action To determine the systemic action, rootedbean plants Ciii" 3 1 6124 (Vicia fabae) were put into a 0.01% aqueousactive substance solution (obtained from a 10% emulsifiable 40concentrate). After 24 hours, aphide (Aphis fabae) L H were placed onthe parts of the plant above the soil. 2 5 The aphids were protectedfrom contact and gas action SCH by means of a special device. The testwas carried out 2 5 24C nd 70C r l tive humidit In the ab ve test at a ea y o the compounds according to Example 1 have systemic action againstAphis fabae.

EXAMPLE 3 ClQCiI-i' 20 Action against Chilo suppressalis S D ,594 Sixrice plants at a time of the variety Caloro were l transplanted intoplastic pots (diameter at the top 17 O=P OC H cm) and reared to a heightof about 60 cm. Infestation 2 5 with Chilo suppressalis larvae (L,: 3-4mm long) took S-CH place 2 days after the active substance had been ap-J plied in granule form to the paddy water (rate of application: 8 kg ofactive substance per hectare). Evaluation of the insecticidal actiontook place 10 days after application of the granules. The compoundsaccording C] H 20 to Example 1 were active in the above test against C nl 5 93 suppressalis.

i EXAMPLE 4 O=|OC H '65 Action against ticks j fl I A. Rhlplcephalusbursa Five adult ticks and 50 tick larvae were counted into a glass tubeand immersed for l to 2 minutes in 2 ml of an aqueous emulsion from anemulsion series each containing 100, I0, 1 or 0.1 ppm of test substance.The tube was then sealed with a standard cotton wool plug and placed onits head, so that the active substance emulsion could be absorbed by thecotton wool.

in the case of the adults evaluation took place after 2 weeks, and inthat of the larvae after 2 days. Each test was repeated twice. I 1 B.Boophilus microplus (larvae) Tests were carried out in each case with 20OP- sensitive larvae using a dilution series analogous to that of testA. (The resistance refers to the tolerability of Diazinon). Thecompounds according to Example I acted in these tests against adults andlarvae of Rhipicephalus bursa and sensitive and OF-resistant larvae ofBoophilus microplus.

EXAMPLE 5 Acaricidal action Phaseolus vulgaris (dwarf beans) have aninfested piece of leaf from a mass culture of Tetranychus urticqe placedon them 12 hours before the test for the acaricidal action. The mobilestages which have invaded the plants are sprayed with the emulsifiedtest preparations from a chromatography atomiser so that the spray brothdoes not run off. The number of living and dead larvae, adults and eggsare evaluated after 2 to 7 days under a stereoscopic microscope and theresult expressed in percentages. During the waiting time", the treatedplants are kept in greenhouse compartments at 25C. The compoundsaccording to Example 1 were active in the above test against eggs,larvae and adults of Tetranychus urticae.

EXAMPLE 6 Action against soil nematodes To the test against soilnematodes, the active substance in the respective concentration isapplied to and intimately mixed with soil infected with root gallnematodes (Meloidgyne Arenaria). Immediately afterwards, tomato cuttingsare planted in the prepared soil in a series of tests and after awaiting time of 8 days tomato seeds are sown in another test series. Inorder to assess the nematocidal action, the galls present on the rootsare counted 28 days after planting and sowing respectively. In this testthe compounds according to Example 1 display good action againstMeloidgyne arenaria.

8 I claim: 1. A compound of the formula wherein R representsethylthiomethyl or propargyl; and each of R R and R represents hydrogen,chlorine or methoxy.

2. The O-ethyl-S-propargyl-S-diphenylmethyldithio- I phosphoric acidester according to claim 1.

3. The O-ethyl-S-methylthiomethyl-S- diphenylmethyl-dithiophosphoricacid ester according to claim 1. a

4. A compound of the formula s. TheO-ethyl-S-(n)-propyl-S-3,4,4-trichlorodiphenylmethyl-dithiophosphoricacid ester according to claim4.

1. A COMPOUND OF THE FORMULA
 2. TheO-ethyl-S-propargyl-S-diphenylmethyldithiophosphoric acid esteraccording to claim
 1. 3. TheO-ethyl-S-methylthiomethyl-S-diphenylmethyl-dithiophosphoric acid esteraccording to claim
 1. 4. A COMPOUND OF THE FORMULA
 5. TheO-ethyl-S-(n)-propyl-S-diphenylmethyldithiophosphoric acid esteraccording to claim
 4. 6. TheO-ethyl-S-(n)-propyl-S-4-chlorodiphenylmethyldithiophosphoric acid esteraccording to claim
 5. 7. TheO-ethyl-S-(n)-propyl-S-4,4''-dichlorodiphenylmethyl-dithiophosphoricacid ester according to claim
 4. 8. TheO-ethyl-S-(n)-propyl-S-3,4,4''-trichlorodiphenylmethyl-dithiophosphoricacid ester according to claim 4.